Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
  • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
  • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
  • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
  • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/20—Heterocyclic amines; Salts thereof
  • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
  • C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring

Definitions

• the present invention relates to novel tertiary amines which are useful as catalyst for producing flexible and rigid foams and elastomers of polyurethane. More particularly, this invention relates to novel amine catalysts which contain a hydroxyl group and are odorless and excellent in the urethane forming reaction when used for producing polyurethane.
• tertiary amines provide a good catalyst for producing polyurethane.
• a tertiary amine having a hydroxyl group such as dimethylethanolamine, has been used as catalyst for producing polyurethane.
• dimethylethanolamine has a degree of volatility with emission of an offensive odor, and also has disadvantages such as insufficient catalytic activities in the uretane forming reaction and cure.
• the present inventors noticed the utility of tertiary amines having a hydroxyl group and intensively investigated for catalyst free from those disadvantages mentioned above. Thus, the present inventors finally succeeded in developing a novel amine catalyst which is odorless and excellent in the urethane forming reaction.
• the novel catalyst of the present invention features pronounced activity in accelerating the urethane forming reaction for the production of polyurethane.
• the catalyst of this invention can be applied as catalyst for producing polyurethane from polyester polyol, for which morpholine catalysts have been hitherto used.
• Some kinds of the morpholine catalysts are known as being toxic. Therefore, use of the catalyst of the present invention can contribute to solve the problem of toxicity inherent to morpholine catalysts. It has been revealed, as an additional advantage, that the catalyst of this invention is possessed of the property as a thermo-sensitive catalyst in that the activity of this catalyst is increased when the temperature is increased as the chemical reaction progresses in the production of polyurethane.
• Another feature of the novel catalyst of the present invention is that a flexible urethane foam prepared in the presence of the catalyst of this invention exhibits a small residual strain on wet compression set at the elevated temperature.
• a practical problem has often been confronted with that when a tertiary amine having a hydroxyl group, such as dimethylethanolamine, is used as catalyst, the residual strain on wet compression set at the elevated temperature which is an important physical property of a urethane foam, increases.
• a very small residual strain on wet compression can be obtained at the elevated temperature when the catalyst of this invention is used.
• This fact explicitly demonstrates that the use of catalyst of the present invention provides a urethane foam having good elongation properties without sacrificing any other property.
• An additional feature of the novel catalyst of this invention is that it is odorless. This is due to the high boiling point, hence a relatively low volatility, of the catalyst and secondly due to the reactive hydroxyl group present in the molecule of the catalyst which makes the catalyst to be confined in the polyurethane resin without emitting offensive odor. This feature is very desirable from the standpoint of improving the working condition as well as preventing public pollution.
• the novel amine catalyst of the present invention is a derivative of piperazine having a hydroxyl group, expressed by the following formula: ##STR2##
• R 1 is a methyl, ethyl or propyl group, preferably a methyl group.
• R 2 is a hydrogen atom, a methyl or ethyl group, preferably hydrogen or methyl.
• the novel catalyst of the present invention can be easily prepared by the known 2-step reaction process.
• the first step reaction is to synthesize N-hydroxyalkylpiperazine by the reaction of piperazine with ethylene oxide, propylene oxide, or butane-1,2-oxide.
• the second step reaction is to convert the above product into a tertiary compound.
• this reaction may be utilized the Leuckart-Wallach reaction described in U.S. Pat. No. 4,026,840 and the reductive methylation reaction disclosed in West German Pat. No. 26 18 580.
• the amount of catalyst to be used in the production of polyurethane is 0.01 to 4 parts, preferably 0.05 to 3 parts, against 100 parts of polyol used.
• the catalyst may be used in combination with triethylenediamine and organic tin compounds which are usually employed as cocatalyst.
• Polyisocyanate used in the production of polyurethane by using the catalyst of this invention is known and may be selected from the group consisting of tolylenediisocyanate, diphenylmethane diisocyanate, polymeric polyisocyanate and aliphatic polyisocyanate.
• polyesterpolyol or polyetherpolyol which includes, for example, polyesterpolyols which are usually derived from a dibasic acid and a polyhydric alcohol, polyetherpolyols which are prepared by the addition reaction of a polyhydric alcohol, such as glycol, glycerine, pentaerythritol trimethylolpropane, and can sugar with ethyleneoxide or propyleneoxide, and amine polyols.
• a foaming agent such as CFCl 3 and CH 2 Cl 2
• a surfactant such as organopolysiloxane
• a flame retardant agent such as halogenated alkyl compounds and halogenated phosphorus compounds
• the solution contained 503 g of unreacted piperazine and 130 g of N-hydroxyethylpiperazine, and 27 g of bis(N-hydroxyethyl)piperazine. 120 g of N-hydroxyethylpiperazine having boiling point from 121° to 123° C. under 10 mmHg was obtained by distillation of this reaction solution.
• the chemical structure was ascertained by the elemental analysis, nuclear magnetic resonance spectrum, and mass spectrum analysis.
• N-(2-hydroxypropyl)piperazine which was synthesized in Example for Reference 2 was recited to obtain N-methyl-N'-(2-hydroxypropyl)piperazine having a boiling point at 135° C. under 20 mmHg.
• the chemical structure was ascertained by the elemental analysis, nuclear magnetic resonance spectrum and the mass spectrum analysis.
• a urethane foam with good elongation property could be produced without increasing the residual strain on wet compression set at the elevated temperature, in comparison with the product in Example for Reference 1.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polyurethanes Or Polyureas (AREA)

Applications Claiming Priority (2)

Related Parent Applications (1)

Publications (1)

Family

ID=12696608

Family Applications (1)

Country Status (3)

Cited By (11)

Families Citing this family (3)

Citations (4)

• 1982
  • 1982-03-23 JP JP57044625A patent/JPS58162625A/ja active Granted
• 1983
  • 1983-03-21 DE DE3310124A patent/DE3310124A1/de active Granted
• 1985
  • 1985-06-24 US US06/748,140 patent/US4590223A/en not_active Expired - Lifetime

Patent Citations (4)

Also Published As

Similar Documents

Legal Events